CN102336922A - Method for preparing high performance anion-exchange membrane through plasma copolymerization - Google Patents
Method for preparing high performance anion-exchange membrane through plasma copolymerization Download PDFInfo
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- CN102336922A CN102336922A CN2011103135596A CN201110313559A CN102336922A CN 102336922 A CN102336922 A CN 102336922A CN 2011103135596 A CN2011103135596 A CN 2011103135596A CN 201110313559 A CN201110313559 A CN 201110313559A CN 102336922 A CN102336922 A CN 102336922A
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- exchange membrane
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a method for preparing a high performance anion-exchange membrane through plasma copolymerization. The method comprises the following steps of: discharging by using plasmas to perform plasma treatment on gas and gaseous functional monomers so as to generate various active ingredients; and performing addition, polymerization and quaterisation between the active ingredients or between the active ingredients and monomers, and depositing to obtain the anion-exchange membrane. The anion-exchange membrane is directly deposited on an electrode catalyst layer, the poisoning effect of the subsequent quaterisation process on an electrode catalyst is avoided, and a preparation process for the anion-exchange membrane can be simplified; and the prepared anion-exchange membrane has high thermal stability, chemical stability and ionic conductivity, and is suitable for polymer electrolytic fuel batteries.
Description
Technical field
The present invention relates to the preparation method that a kind of plasma body copolymerization prepares the high-performance anion-exchange membrane, be specifically related to the preparation method of a kind of polymer electrolyte fuel cells with the basic anion exchange membrane.
Background technology
Be that the polymer electrolyte fuel cells of representative has characteristics such as cleaning, efficient, cold operation with the Proton Exchange Membrane Fuel Cells; It is a kind of fuel cell that has development potentiality and using value; Yet, the sour environment that fuel cell is worked require to use cost an arm and a leg and the precious metals such as platinum of scarcity of resources as catalyzer, make the battery cost increase [R. Borup greatly; Et al., Chem. Rev. 107 (2007) 3904].In order to address this problem the basic anion exchange film fuel battery employing basic anion exchange membrane that grows up is ionogen, conduction hydroxide ion (OH
–) Working environment is alkalescence, need not to use precious metal such as platinum as catalyzer, and the CO that is not easy to take place catalyzer poisons, because OH
–The infiltration of conduction orientation and fuel in the opposite direction, battery fuel sees through phenomenon not serious [C. Coutanceau, et al., J. Power Sources 156 (2006) 14; J.R. Varcoe, et al., Fuel Cells 5 (2005) 187; K. Kordesch, et al., J. Hydrogen Energ. 13 (1988) 411].The core of alkaline direct alcohol fuel cell is basic anion exchange membrane (AAEM), and it has played conduction OH
–, isolated electronics, stop fuel and oxygenant to see through triple role, its performance will influence fuel cell performance to a great extent.
Though about the existing a lot of reports of the method for basic anion exchange membrane preparation, the overwhelming majority has all only been considered the performance of film itself, and the problem that possibly exist after film and the electrode assembling is seldom inquired into.In fact; Film, electrode prepare back static pressure method (or pressure sintering) the component film electrodes that adopt separately more; Do not cause catalyst utilization not high because of contacting fully between electrode catalyst particle and the film; Problems [ChemPhysChem 1 (2000) 162 for L. Carrette, et al.] such as film and electrode contact resistance are bigger.The using plasma polymerization prepares the basic anion exchange membrane; Film directly is deposited on the electrode catalyst layer, film and electrode are combined closely, can not only reduce the contact resistance between film and the electrode; Can also increase phase reaction district area; Improve the utilization ratio [C. Zhang, et al., J. Power Sources 196 (2011) 5386] of electrode catalyst.Yet; The quaternized process need that directly is deposited on the plasma polymerization film on the electrode is soaked in 48 h in the trimethylamine solution to membrane electrode; There is poisoning effect [C. Zhang, et al., Chem. Commun. doi:10.1039/c1cc11888.a] in trimethylamine solution counter electrode catalyzer.Simultaneously, quaternised anionresin membrane prepare process is unfavorable for the formation of effective ion passage in the film after the first film forming, hinders OH
–Conduction [Macromolecules 43 (2010) 2349 for J. Yan, et al.].
Summary of the invention
In order to overcome the deficiency of prior art, the invention discloses the preparation method that a kind of plasma body copolymerization prepares the high-performance anion-exchange membrane.Utilize plasma discharge gas, gaseous state functional monomer plasma bodyization; Make and produce all kinds of active species; Carry out addition, polymerization, quaterisation subsequently between the active specy or between active specy and the monomer; Formation of deposits has the anion-exchange membrane of higher functionality group content, and anion-exchange membrane makes after alkalization has OH
–The basic anion exchange membrane of transmissibility.
The present invention adopts following technical scheme to achieve these goals:
The plasma body copolymerization prepares the method for high-performance anion-exchange membrane, it is characterized in that may further comprise the steps:
(1) reaction cavity vacuumizes, and logical reaction gas is to reactor drum, makes that pressure reaches 20-22Pa in the chamber in, lasting 4-5 min;
(2) conditioned reaction airshed, making the interior pressure values of cavity is 10Pa and constant 2-3min, feeds monomer 1 and monomer 2 respectively; Total pressure is 40-80 Pa in the cavity, and the pilot-gas flow makes the monomer 1 and the intrinsic standoff ratio of monomer 2 be (0.1-10): 1; Regulate radio-frequency power supply; Discharge power is 20-60 W, and plasma polymerization 1-6 h makes plasma body copolymerization anion-exchange membrane;
(3) anion-exchange membrane that step (2) is made is soaked in the 1-2 mol/L alkaline solution, and soak time 12-60 h after alkalization is good takes out film, and deionized water wash, immersion promptly obtain the basic anion exchange membrane.
The plasma body copolymerization prepares the method for high-performance anion-exchange membrane, it is characterized in that: described monomer 1 is selected from a kind of in vinyl pyridine, the Trimethylamine 99, and described monomer 2 is a benzyl chloride base ethene.
The plasma body copolymerization prepares the method for high-performance anion-exchange membrane, it is characterized in that: said reaction gas is a kind of in argon gas, helium, nitrogen, the hydrogen.
The plasma body copolymerization prepares the method for high-performance anion-exchange membrane, it is characterized in that: said alkaline solution is selected from a kind of in alkali hydroxide soln, the alkaline earth metal hydroxides solution.
Beneficial effect of the present invention:
(1) the inventive method plasma polymerization and quaterisation take place simultaneously, help the separation of microfacies structure in the film and the formation of ionic channel;
(2) anion-exchange membrane that makes of the inventive method has thermostability, chemicalstability preferably, and higher ionic conductivity is applicable to polymer electrolyte fuel cells;
(3) the inventive method can directly be deposited on anion-exchange membrane on the electrode catalyst layer, prepares fuel cell integrated membrane electrode, can avoid the poisoning effect of follow-up quaternized process counter electrode catalyzer, can also simplify the preparation technology of anion-exchange membrane.
Description of drawings
Fig. 1 schematic flow sheet of the present invention.
The cross section TEM photo of Fig. 2 plasma body copolymerization film.
A Fig. 3 plasma body copolymerization basic anion exchange membrane (PCPNOH) and day OH of Bender mountain products commercialization anion-exchange membrane (AHA-OH)
–Specific conductivity concerns with variation of temperature.
Embodiment
Embodiment 1:The plasma body copolymerization prepares the method for high-performance anion-exchange membrane, may further comprise the steps:
(1) reaction cavity vacuumizes, and logical argon gas is to reactor drum, makes that pressure reaches 20 Pa in the chamber in, lasting 5 min;
(2) regulate argon flow amount, making the interior pressure values of cavity is 10Pa and constant 2 min, feeds monomer ethylene yl pyridines and monomer benzyl chloride base ethene respectively; Total pressure is 40-80 Pa in the cavity, and the pilot-gas flow makes the intrinsic standoff ratio of monomer ethylene yl pyridines and monomer benzyl chloride base ethene be (0.1-10): 1; Regulate radio-frequency power supply; Discharge power is 20-60 W, and plasma polymerization 1-6 h makes plasma body copolymerization anion-exchange membrane;
(3) anion-exchange membrane that step (2) is made is soaked in the 1-2 mol/L sodium hydroxide solution, and soak time 12-60 h after alkalization is good takes out film, and deionized water wash, immersion promptly obtain the basic anion exchange membrane.
Embodiment 2:As shown in Figure 1, answer cavity to vacuumize, logical argon gas is to reactor drum, makes that pressure reaches 20 Pa in the chamber in, lasting 5 min; Regulate argon flow amount, making the interior pressure values of cavity is 10 Pa and constant 2 min, feeds vinyl pyridine and benzyl chloride base ethene respectively; Total pressure is 60 Pa in the cavity, the pilot-gas flow, and making the intrinsic standoff ratio of vinyl pyridine and benzyl chloride base ethene is 1; Regulate radio-frequency power supply; Discharge power is 20 W, and plasma polymerization 3 h make plasma body copolymerization anion-exchange membrane; The anion-exchange membrane that makes is soaked in the 2 mol/L alkaline solutions, and soak time 48 h after alkalization is good take out film, and deionized water wash, immersion promptly obtain the basic anion exchange membrane.Fig. 2 is the cross section TEM photo of plasma body copolymerization film; Can find out between the ionic group bunch through Fig. 2 and to be connected to each other; Form passage, the diameter of ionic channel is about 20 nm, shows that the plasma body copolymerization process can successfully realize the separation of microfacies structure in the film; Promote the formation of ionic group bunch and ionic channel, the formation of ionic channel will help increasing the OH of basic anion exchange membrane
–Transmissibility.Fig. 3 is plasma body copolymerization basic anion exchange membrane (PCPNOH) and Japanese NEOSEPTA
Produce the OH of commercialization anion-exchange membrane (AHA-OH)
–Specific conductivity concerns with variation of temperature, can find out OH in PCPNOH and two kinds of films of AHA-OH through Fig. 3
–Specific conductivity all increases along with the rising of temperature, and under the uniform temp, the specific conductivity of plasma body copolymerization basic anion exchange membrane (PCPNOH) is apparently higher than commercialization anion-exchange membrane (AHA-OH).
Claims (2)
1. a plasma body copolymerization prepares the method for high-performance anion-exchange membrane, it is characterized in that may further comprise the steps:
(1) reaction cavity vacuumizes, and logical reaction gas is to reactor drum, makes that pressure reaches 20-22Pa in the chamber in, lasting 4-5 min;
(2) conditioned reaction airshed, making the interior pressure values of cavity is 10Pa and constant 2-3min, feeds monomer 1 and monomer 2 respectively; Total pressure is 40-80 Pa in the cavity, and the pilot-gas flow makes the monomer 1 and the intrinsic standoff ratio of monomer 2 be (0.1-10): 1; Regulate radio-frequency power supply; Discharge power is 20-60 W, and plasma polymerization 1-6 h makes plasma body copolymerization anion-exchange membrane;
(3) anion-exchange membrane that step (2) is made is soaked in the 1-2 mol/L alkaline solution, and soak time 12-60 h after alkalization is good takes out film, and deionized water wash, immersion promptly obtain the basic anion exchange membrane;
Described monomer 1 is selected from a kind of in vinyl pyridine, the Trimethylamine 99, and described monomer 2 is a benzyl chloride base ethene, and said reaction gas is a kind of in argon gas, helium, nitrogen, the hydrogen.
2. plasma body copolymerization according to claim 1 prepares the method for high-performance anion-exchange membrane, it is characterized in that: said alkaline solution is selected from a kind of in alkali hydroxide soln, the alkaline earth metal hydroxides solution.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104798234A (en) * | 2012-12-28 | 2015-07-22 | 日东电工株式会社 | Fuel cell membrane-electrode assembly and method for manufacturing same, and fuel cell |
| CN106654327A (en) * | 2016-12-12 | 2017-05-10 | 成都育芽科技有限公司 | Anion exchange membrane for new energy fuel cells and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1687149A (en) * | 2005-02-01 | 2005-10-26 | 中国科学院等离子体物理研究所 | Method of plasma for initiating polymerization of vinyl monomer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1687149A (en) * | 2005-02-01 | 2005-10-26 | 中国科学院等离子体物理研究所 | Method of plasma for initiating polymerization of vinyl monomer |
Non-Patent Citations (1)
| Title |
|---|
| 《Journal of Powder Sources》 20111001 Zhang Chengxu 等 Microphase separated hydroxide exchange membrane synthesis by a novel plasma copolymerization approach 第113页2.2节 第198卷, * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104798234A (en) * | 2012-12-28 | 2015-07-22 | 日东电工株式会社 | Fuel cell membrane-electrode assembly and method for manufacturing same, and fuel cell |
| CN104798234B (en) * | 2012-12-28 | 2017-11-07 | 日东电工株式会社 | Membrane-membrane electrode for fuel cell component, its manufacture method and fuel cell |
| CN106654327A (en) * | 2016-12-12 | 2017-05-10 | 成都育芽科技有限公司 | Anion exchange membrane for new energy fuel cells and preparation method thereof |
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Application publication date: 20120201 |